Polyesters of dicarboxyphenyldimethylsilane



Patented June 24, 1952 POLYESTERS OF DICARBOXYPHENYLDI- METHYLSILAN E Leslie J. Tyler, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich.,' a corporation of Michigan 4 Claims. (01. 260-75) This invention relates to polyesters of carboxyphenylsilanes and polyhydric alcohols.

It is an object of this invention to prepare novel compositions of matter of the polyester linked infusible gel may be obtained.

The polyester materials herein described withstand temperatures in excess of 165 C. without deterioration. They show excellent adhesion to glass and to metals and have good type which are useful as coating compositions 5 weathering characteristics. This combination for glass and for electrical conductors and as of properties render the materials applicable for paint vehicles. use as paint vehicles both at natural tempera- This invention relates to polyesters of ditures and at elevated temperatures. carboxyphenyldimethylsilane and polyhydric al- The polyesters containing an excess of either cohols selected from the group consisting of hydroxyl or carboxyl groups may be modified by ethylene glycol, glycerol and bis-hydroxymethreacting them with other hydroxyl, carboxyl or yldimethylsilane, wherein the silane polymer amino containing materials. units are linked to the alcohol polymer units by The following examples are illustrative only.

Example 1 I 1 g. of dioarboxyphenyldimethylsilane linkages. In the polyester the proportion of alcohol to silane varies from one mol of alcohol (HOOCC6H4)2S1(CI'I3)2 per three mols of silane to one mol of alcohol was mixed with 1 g. of bis-hydr xym y per 0.306 mols of silane. methylsilane and heated at 135 C. for 2 hours.

The preparation of dicarboxyphenyldimethylhe resulting polyester was a viscous oil. silane is more fully described in the applicants A sample of the polyester was placed on a copending application filed concurrently hereglass slide and heated 3 hours at 160 C. The with, now Patent No. 2.517.146. The silane may liquid polym r d to a th rm pla i s lid which conveniently be prepared by making a Grignard Was hard and tough a d Strongly a t to reagent of dibromophenyldimethylsilane and lassthereafter carbonating the organomagnesium Example 2 compound and then acidifying the material.

Ethylene glycol and glycerol are well-known 1.5 g. of dicarboxyphenyldimethylsilane, 0.6 g. products. Bis-hydroxymethyldimethylsilane may 0f biS-hydr0Xymethyldimethylsilane d -6 be prepared according to the method of John of glycerol were mixed and heated at 135 C. for L. Speier, Journal American Chemical Society, 3 hours. The resulting polyester was a light vol. 70, page 1400 (1948). brown, opaque, thermoplastic material. A sam- The polyesters of this invention are prepared ple of the po yester was heated at 160 C. for 3 by mixing the silane and the alcohols and therehours on a glass slide. A thermoplastic resinous after heating ithe mixture at a temperature from material was obtained. 90 C. to 200 C. Reaction takes place between Emam l6 3 the oarboxyl groups of the silane and the alcop hol hydrox'yl..groups to produce polyesters with 1.5 g. of dicarboxyphenyldimethylsilane and the elimination of water. If desired, small 1.5 s- Of lycerol were mixed and heated at 135 amounts of strong acids may be employed as 40 C. fore hours and at 160 C. for 1 hours. The catalysts for the reaction. When catalysts are resulting polyester was a, soft thermoplastic solid. employed, reaction temperatures below C. A sample of the polyester was heated on a glass are feasible. When the reaction temperature is slide at 160 C. for 3 hours whereupon a hard. below 0., it is desirable to employ reduced tough, thermoplastic resin was obtained. pressure in order to facilitate the removal of 5 Waten Example 4 The polyesters of this invention may be fluids. 1.5 g. of dicarboxyphenyldimethylsilane and 1 thermoplastic resins or infusible'thermoset gels. g. of ethylene glycol were mixed and heated 2 The type of product obtained varies with the hours at C. and 1 hours at C. The degree of functionality of the reactants employed 50 resulting polyester was a soft, thermoplastic solid and the proportions of the reactants. which melted to a clear liquid below 160 C. A

When both of the reactants are difunctional, sample of the polyester was placed on a glass the polymers will be liquids or thermoplastic slide and heated 3 hours at 160 C. whereupon a Solids- When the sila e is reacted Wit glycer hard, brittle, thermoplastic resin was produced. in approximately equimolar amounts, a cross- 55 Th t whi h i l i d i 1. A polyester composed of the esterification product of dicarboxyphenyldimethylsilane and a polyhydric alcohol selected from the group consisting of ethylene glycol, glycerol, and bis-hydroxymethyldimethylsilane, in which polyester the proportion of alcohol to dicarboxyphenyldimethylsilane is from one mol of alcohol per three mole of dicarboxyphenyldimethylsilane to one mol of alcohol per 0.306 mol of dicarboxyphenyldimethylsilane.

2. A polyester in accordance with claim 1 in which the alcohol is ethylene glycol.

3. A polyester in accordance with claim 1 in which the alcohol is glycerol.

4. A polyester in accordance with claim 1 in which the alcohol is bis-hydroxymethyldimethylsilane.

LESLIE J. TYLER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Ellis Aug. 14, 1934 Number 

1. A POLYESTER COMPOSED OF THE ESTERIFICATION PRODUCT OF DICARBOXYPHENYLDIMETHYLSILANE AND A POLYHYDRIC ALCOHOL SELECTED FROM THE GROUP CONSISTING OF ETHYLENE GLYCOL, GYCEROL, AND BIS-HYDROXYMETHYLDIMETHYLSILANE, IN WHICH POLYESTER THE PROPORTION OF ALCOHOL TO DICARBOXYPHENYLDI METHYLSILANE IS FROM ONE MOL OF ALCOHOL PER THREE MOL OF DICARBOXYPHENYLDIMETHYLSILANE TO ONE MOL OF ALCOHOL PER 0.306 MOL OF DICARBOXYPHENYLDIMETHLSILANE. 